CHROMIUM, FERROCHROMIUM, AND FERROCHROMIUM-SILICON A.

Commodity Summary

Chromite ore, the sta rting material for chrom ium metal, alloys, and other chromium produ cts, is not produced in the United States. 1 The metallurgical and chemical industry consumed 93 percent of the imported chromite ore used domestically in 1994; the refractory industry consumed the remainder. The major end uses of chromium metal and ferroalloys were stainless and heat-resisting steel (78 percent), full-alloy steel (8 percent), superalloys (2 percent) and other miscellaneous uses (12 percent).2 Exhibit 1 summa rizes the produc ers of chromium p roducts in 1992. O nly a small amount of the chromite is processed to produce ductile chromium; the rest is used in an intermediate form.3 EXHIBIT 1 SU M M A R Y
OF

PRODUCERS

OF

C H R O M IU M P RODUCTS ( I N 1992) a Location Corpus Christi, TX Marietta, OH Alloy, WV Lehi, UT Industry Chemical Metallurgical Metallurgical Refractory Refractory Metallurgical Refractory Refractory Refractory Chemical Metallurgical

Facility Name American Chrome & Chemicals Inc. Elkem AS, Elke m Metals Co. Elkem AS, Elke m Metals Co. General R efractories Co. Harbison-Walker Refractories Macalloy Corp. National Refractories and Mining Corp. National Refractories and Mining Corp. North American Refractories Co. Ltd. Occidental Chemicals Corp. Satra Concentrates Inc.
a b

b

Hammond, IN Charleston, SC Moss Landing, CA Columbiana, OH Womelsdorf, PA Castle Hayne, NC Steubenville, OH

- Papp, John. "Chromium," Minerals Yearbook Volume 1. Metals and Minerals 1992. United States Bureau of Mines. 1992. p. 355. - a division of Dresser Industries Inc.

Ferrochromium , an alloy of iron and chrom ium, is used as an a dditive in steel making. Th ere are three major grades of ferrochromium: low carbon, high carbon, and charge grade. In the past, low carbon ferrochromium was required by steel makers to keep the carbon content of steel low. However, improved ladle refining techniques such as argon oxygen decarburization, have allowed the steel industry to use high carbon ferrochromium, which is less expensive.4

John Papp, "Chromium," from Mineral Commodity Summaries, U.S. Bureau of Mines, 1995, p. 43.
2

1

Ibid, p. 42.

"Chromium and Chromium Alloys," Kirk-Othmer Encyclopedia of Chemical Technology, 4th ed., Vol. VI, 1993, p. 230. John Papp, "Chromium," Minerals Yearbook Volume 1. Metals and Minerals 1992, U.S. Bureau of Mines, 1992, p. 325.
4

3

and aluminosilicates) and a carbonaceous reductant (wood chips. Discussion of Typical Production Processes Chromite ore is prepared for processing using several methods. alloy. 327.7 Ferrochromium-silicon typically contains 34 to 42 percent chromium... 234. Lumpy ore mixed with host rock may require hea vy-media separation. Cit. Generalized Process Flow Diagram Ferrochromium Ferrochromium is made by smelting chromite ore in an electric arc furnace with flux materials (quartz. Either ferrochromium or sodium chromate is produced. no ferrochromium-silicon has been produced in the United States since 1982. Metallurgy. Cit.Ferrochromium-silicon is used in the metallurgical industry to produce stainless. dolomite. Although a high silicon f errochromium is som etimes produce d as an interme diate in the produc tion of low carbon ferrochromium. and may be sold or further processed to manufacture other chromium c ompounds. Op. 11 10 John Papp. furnace dust is collected and resmelted." Industrial Minerals and Rocks. In efficiently operated smelters. Course clean ore is hand sorted. p. 1992. 141. p. Ibid. 328.S. hence many of these operations may not be conducted in the United States. 11 The production of low carbon ferrochromium requires 5 John Papp. .) Lumpy ore may be fed direc tly to the furnace. limestone." 1993. coke. p. p. 210.. 10 Exhibit 2 is a conceptual diagram of chromite ore processing.8 B. 232. Society for Mining. Op.. p.05 to 0. p.6. "Chromite. and tool steels and cast irons. Personal Communication between ICF Incorporated and John Papp. while fine clean ore is gravity separated. and slag is crushed and processed to recover chromium. while fin er ore must be agglom erated before it is added to the furna ce. silicon is add ed during the sme lting process. 8 9 John Papp. 2. March 1994. U. Cit. Generalized Process Description 1. Bureau of Mines. If the chromite minera l occurs in fine grains intermixed with host roc k. as we ll as chromium meta l. 1985.06 percent carbon. Op.5 Ferrochromium-silicon is a smelted produc t of chromite ore. 1994. 38 to 45 percent silicon and 0. 7 6 "Chromium and Chromium Alloys.S. or charcoal. "Chromium. Bureau of Mines. crushing. U. depending on the ore source and the end use requirements.9 Chromite ore is typically beneficiated before it is sold. 1992." Mineral Facts and Problems. and Exploration. The chromium conte nt of the ferrochrom ium is determined by the chromite ore's chr omium to iron ratio. John Papp. and it is unlikely to be produced domestically again. gravity separation and magnetic separation may be used. 6th Ed.

EXHIBIT 2 C ONCEPTUAL D I A G R A M OF C HROMITE O RE P R O C E S S IN G Graphic Not Available. p. . Source: Kirk-Othmer E ncyclopedia of Ch emical Tech nology. 1993. 233.

The reacted material is slurried with water and washed. Report to Congress on Special Wastes from Mineral Processing. II. EPA. 1978. that is.top blowing with oxygen. and the resultant slurry is heated in a kiln. Company Responses to the "National Survey of Solid Wastes from Mineral Processing Facilities". 275. Vol.S. and are therefore outside the scope of this report. The material recovered from the kiln is slurried with water.15 The alumina-fr ee sodium chrom ate may be marke ted.. Brief descriptions of these processes have been included for completeness. silicon is used as the reducing agen t. Environmental Protection Agency. and sold as a solid. p.12 Sodium Chroma te and Dichromate Sodium chromate and dichromate are produced at two facilities by a hydrometallurgical process during which ground chrome ore and soda ash are mixed (lime and/or leached calcine are sometimes added as well). screened and packaged. Occidental Chemicals Corp. Most of the washwater from the process is treated with sulfuric acid to recover boric acid.13 The resulting leach liquor is separated from the remaining leach residue. ground.S. U. sulfur and wheat flour are blended with water. p. August 1980. NY. Versar. p. in which high carbon ferrochromium and oxidized ferrochromium are heated unde r high vacuum. Marks. 232. July 1990. Environmental Protection Agency. 13 American Chrome and Chemicals and Occidental Chemical.3-16. pp. 233. and leached with weak chromate liquor or water. U. uses a continuous process that involves treatment with sulfuric acid. Office of Solid Waste. dried. two complete chromium extraction cycles are performed prior to removal of the residue. 93-94. 4-2. Extremely low carb on ferrochromium is made by the simplex process. Wiley Interscience. et al. Processing of either form of chromic oxide.) This pr ocess confers the advantage of not gen erating a sludge. the roasting/leaching sequence is repeated. pp. as shown in Exhibit 3. editors. 18 17 16 15 14 .S. it is disposed on-site at both facilities. The product with some of the final washwater is filtered. Volume II. Th e carbon and oxygen form carbon monoxide. Op. 3-13 . At the American Chrome and Chemicals facility. Source: Kirk-Othmer E ncyclopedia of Ch emical Tech nology. Inc.) Sodium sulfate may be sold as a byproduct or disposed. Th e dichromate liquor may be sold as 69 percent sodium dichromate solution or returned to the evaporators.16 Chromium Oxide Sodium dichromate can be converted into both anhydrous chromic oxide and hydrated chromic oxide. leaving a p ure ferrochrom ium with a carbon content of about 0. or more fre quently. The treatmen t residue from this ope ration is classified as a RCRA special waste. 1993. Ibid. crystallized. 1989. Encyclopedia of Chemical Technology.. Alu minum. and precipitation of sodium sulfate (see left output stream from leaching and precipitation operation in Exhibit 3. p. but the predom inant practice is to con vert the chromate to the dichromate form. roasted in an oxidizing atmosphere. as well as chromium metal are not primary mineral processing. this liquor is neutralized and then filtered (not shown) to remove metal precipitates (primarily alumina hydrate). rewashed. A waste stream containing boric acid and sodium sulfate leave the boric acid recovery unit. filtered. a s discussed below . 1989. Industrial Environmental Research Laboratory. sodium dichromate.. ground to size.17 To produce anhydrous chromic oxide (not shown).01 weight percen t.. screened and packaged. evaporation of sodium dichromate. Th e leach residu e is then treated.14 The leach solution contains unrefined sodium chromate. New York. dried." 1993. Cit. To produce hydrated chromic oxide (not shown). Prepared for U. Multi-Media Assessment of the Inorganic Chemicals Industry. sodium dichromate solution and boric acid are blended and heated in a kiln.18 Chromium Metal 12 "Chromium and Chromium Alloys. American Chrome and Chemicals uses carbon dioxide (CO2) to convert the chromate to dichromate (see right output stream from leaching and precipitation opera tion in Exhibit 3. washed.

b ecause EP A has determ ined that all operations following the initial "process ing" step in the produ ction 19 "Chromium and Chromium Alloys. processing activities often destroy the physical and chemical structure of the incoming ore or mineral feedstock such that the materials lea ving the operation do not close ly resemble those that e ntered the oper ation. chromium oxide (Cr2O 3) reacts with alum inum powder in a refractory lined vesse l after being ignited with barium peroxid e and magne sium powder. and the metal is rem oved by air hammers. This iron salt is further treated to form technical ferrous ammonium sulfate. The filtrate is conditioned at elevated temperature for several hours to convert the chromium to the non-alum form. Beneficiation a ctivities generally do not cha nge the mineral va lues themselves othe r than by reducing ( e. generally follow beneficiation and serve to change the concentrated mineral value into a more useful chemical form. which can be sold as fertilizer and other purposes. and waste generation points and quantities presented above in Section B. The filtrate is clarified and aged. and the slurry is filtered to remove the undissolved solids. EPA reviewed the detailed process flow diagram(s).. This is often done by using heat (e. which are mostly silica. Ferrochromium EPA determined that for ferrochromium. 3661 6 codified at 261.E. 20 J. smelting) or chemical reactions (e. allowing a crude ammonium sulfate to crystallize. p. R eg. Mineral processing operations. 234-236. pp. In essenc e. Cold mother liquor is a dded. except the aluminum content is lower and the silicon content may approach 0. The chromium from this process is similar to that obtained by the aluminothermic process.21 4. Beneficiation/Processing Boundaries EPA established the criteria for determining which wastes arising from the various mineral production sectors come from miner al processing opera tions and which a re from benef iciation activities in the Sep tember 1989 final rule (see 54 Fed.. Goodwill." 1993. Source: Kirk-Othmer E ncyclopedia of Ch emical Tech nology. and in the United States. the functional importance of each step in the production sequence. or enlarging (e. chrome alum mother liquor. Chromium may also be made by reducing chromium oxide briquets with carbon at low pressure and temperatures of 1.g. crushing or grinding). The slurry is filtered. pelletizing or briquetting) particle size to facilitate processing.. Therefore. No. in contrast.. 1993.g. to utilize low quality chromium bearing ores.275 to 1. The filtrate is then cooled to 5°C. To locate the be neficiation/proces sing "line" at a given fa cility within this mineral commodity sector. Ch romium metal may also b e made from the oxide by reduction w ith silicon in an electric arc furnace. the c athodes are re moved.19 Exhibit 4 shows the production of electrolytic chromium by the chrome alum process conducted at the Elkem Metals Company's Marietta Plant. 21 . 5. 17. as nece ssary. beginning with relatively straightforward questions and proceeding into more detailed examination of un it operations. and dehydrogenated. or prepare the ore for further ref inement.4 (b)(7)). p. The metal is crushed. washed . acid digestion.. 352. Cit. and the chrome alum is dissolved in hot water. High carbon ferrochromium is ground and leached with a hot solution of reduced anolyte. allowing ammonium chrome alum to precipitate. remove impu rities. pp. beneficiation wastes are ea rthen in chara cter. beneficiation op erations typically serve to sepa rate and concen trate the mineral va lues from waste m aterial. Typically. as a more efficient way of processing ferrochromium. chlorin ation) to change the chemical comp osition of the mineral. After the electrolysis is complete. Identification/Discu ssion of Nov el (or otherw ise distinct) Process(es) Research is being conducted to investigate the feasibility of using plasma smelting both worldwide.Chromium meta l can be made either pyrometallurgica lly or electrolytically. "Developing Plasma Applications for Metal Production in the USA. 233. Ibid.g. wherea s mineral proces sing wastes are de rived from melting or chemical changes. A chemical change in the mineral value does not typically occur in beneficiation." Iron and Steelmaking.g. and m akeup sulfuric a cid. 36592.. In contra st to beneficiation operations. as well as information on ore type(s). washed. EPA approached the problem of determining which operations are beneficiation and which (if any) are processing in a step-wise fashion. 232-234.8 percent. Op. The chrome alum solution is clarified and fed to the electrolysis cell.400°C. 1990. mineral processing first occurs when the chromite ore undergoes smelting in an electric arc furnace and the physical/ch emical structure of the chromite ore is signific antly altered. In the pyrometallurgical m ethod (not shown).20 3.

please see the sodium chromate/dichromate section above. 1993. all of the wastes generated during chromium oxide production are m ineral processing w astes. mineral pr ocessing occurs a t the "leaching" se quence of the process because the ore is vigorously attacked (digested) with a concentrated acid to significantly change the physical structure of the ore . Therefore. EPA presents below the mineral processing waste streams genera ted after the ben eficiation/processin g line. For a description of where the beneficiation/processing boundary occurs for this mineral commodity. characteristics. and management practices for each of these wa ste streams. characteristics. EPA presents below the mineral processing waste streams ge nerated after the beneficiation/p rocessing line. . along with associate d information on was te generation rates. and management practices for each of these wa ste streams. Sodium Chroma te/Dichromate EPA dete rmined that for sodium chromate/dichr omate. Chromium Metal Since chromium metal is produced from either ferrochromium or chromium oxide. along with a ssociated informa tion on waste genera tion rates. For a descrip tion of where the be neficiation/proces sing boundary occu rs for this mineral commodity. irrespective of whether they involve only techniques otherwise defined as beneficiation. 233. all solid waste s arising from any such operation(s) after th e initial mineral proce ssing operation are considered mineral processing wastes. all solid wastes arising from any such operation(s) after the initial mineral processing operation are considered mineral processing wastes. be cause EPA has determine d that all operations followin g the initial "processing" step in the production sequence are also considered processing operations. irrespective of whether they involve only techniques otherwise defined as be neficiation. rather than beneficiation wastes. please see the ferrochromium and chromium oxide sections above. Source: Kirk-Othmer E ncyclopedia of Ch emical Tech nology. Chromium Oxide Since chromium oxide is produced from sodium dichromate. p. rather than beneficiation wastes.sequence are also considered processing operations. all of the wastes generated during chromium oxide production are mineral processing wastes.

vanadium. Sodium Dichrom ate Production Treated roast/leach residue is classified as a RC RA special w aste. p. U. several other inf luent streams prior to tre atment with severa l different chem ical agents. and zinc. EPA evaluated whether the residue exhibited any of the four characteristics of hazardous waste: corrosivity. though it typically is generated as a slurry containing particle s between 2 mm and about 0. p. chromium.25 The data set lso indicated that approximately 3. 25 24 23 Ibid.23 Using the available data on the composition of treated roast/leach residue. 22 U. as well as lead an d silver.08 m eters (3 inches) in diameter.. We note.26 Additional data is provided in Attachment 1. the data set ndicated that organics were found in the dust or sludge. in which sulfuric acid and sodium sulfide are used to induce the desired chemical changes in the residue. Data from the Newly Identified Mineral Processing Waste Characterization Data Set indicate the ollowing constituents above detection limits for untrea ted and treated K091 (baghou se dust): aluminum . 235. manganese. Extraction and Beneficiation Wastes Wastes from the e xtraction and be neficiation of chrom ite may include gangu e. 26 . Source: Kirk-Othmer E ncyclopedia of Ch emical Tech nology. Newly Identified Mineral Processing Waste Characterization Data Set. p. American C hrome and Ch emicals pumps the leach residu e directly to a dedicate d treatment unit. U. 1993. and chromium.S. selenium. 1989. while at Occidental Chemicals Corp.S. and extraction procedure (EP) toxicity.000 metric tons of dust or sludge are produced annually in the United States. 15-1 . I. the roast/leach residue is not a RCRA special waste. but did not list them by name or concentration. thallium. or was te man ageme nt was a vailab le in the source s listed in the b ibliogra phy. magnesium. aluminum. 1990. Environmental Protection Agency. Treatment of the leach residue consists of treating the residue slurry with either a fer rous or sulfide ion to redu ce hexavale nt chromium followed by treatment with sulfu ric acid to lower the pH leve l. Ibid. the agency did not eva luate this material further. Process Waste Streams 1. The limited available data ind icated that the wa ste did not exhibit any of the four hazardou s waste characteristics. Vol. At both plants. Office of Solid Waste. as well as sulfates. I-3. Cit. Mineral Processing Wastes The following waste streams have been associated with the production of sodium dichromate. Company Responses to the "National Survey of Solid Wastes from Mineral Processing Facilities". Occidental Chemical Corp. pp. and ferrochr omium-silicon.15-10.EXHIBIT 4 C. According to the Newly Identified Mineral Processing Waste Characterization Data Set. such as those of iron.. antimony. molybdenum. In addition. and tailings. magnesium. and apparently comb ines. nickel. that prior to treatmen t. reactivity. Other EP oxicity leachate ana lyses indicated man y of the same constituen ts. No inform ation on waste chara cteris tics. is a solid material. ignitability. August 1992. the untreated residue is pumped to a wastewater treatment plant which receives. Op. the treated residue is pumped in slurry form to disposal surface impoundments. ferrochromium. arium. Environmental Protection Agency. 24 Ferrochromium Dust or Sludge was a listed haza rdous waste that ha s been reman ded.000 metric tons of treated leach residue are produced annually in the United States. EPA.. The treated roast/leac h residue is composed primarily of metallic oxides. I-4. 22 The treated residue from roasting/leaching of chrome ore. wa ste gen eration . silicon. p. howe ver. 4-2. therefore .S. 2. approximately 102.

E L E C T R O L Y TI C C H R O M IU M M ETAL P R O D U C T I O N Source: Kirk-Othmer E ncyclopedia of Ch emical Tech nology. . 1993. 235. p.

therefore .According to the N ewly Identified Min eral Processin g Waste Chara cterization Data Set. and polychlorin ated biphenyls from electr ical tra nsform ers an d capa citors. there is no domestic production of ferrochromium-silicon currently.Slag and Residues . N on-haz ardou s waste s may inc lude tir es from trucks and la rge ma chine ry. D. Other hazardous wa stes may include spe nt solvents. sanitary sewage. 28 . an d waste oil and other lubricants. Ancillary Hazardous Wastes Ancillary haza rdous wastes ma y be generated a t on-site laboratories. 27 Ibid. Ibid. the Agency did not e valuate this material further.28 According to the N ewly Identified Min eral Processin g Waste Chara cterization Data Set. tank cleanin g wastes.27 Ferrochromium -silicon Dust or Sludge was a listed haza rdous waste that ha s been reman ded. and the availab le data do not indicate that the waste is hazardous. approximately 47. Additional data is provided in Attachment 1. and m ay include used c hemicals and liq uid samples.0 00 metric tons of slag an d residue are p roduced ann ually in the United Sta tes.

." From Mineral Commodity Summaries. No. Papp.F. pp. Bureau of Mines. Office of Solid Waste. 5. 1994. Bureau of Mines. 531-542." From Report to Congress on Special Wastes from Mineral Processing. Goodwill. Prepared for U. "Chromium and Chromium Alloys.S. 1. pp. pp.BIBLIOGRAPHY Brown. U. 6th ed. No.S. Bureau of Mines.. pp. U. 4th ed. 42-43." From Mineral Facts and Problems. Katayama. July 1990. J. 42-53. pp. Environmental Protection Agency. "Chromite. H." From Industrial Miner als and Rocks ." From Minerals Yearbook Volume 1. 6. and Smelting of Greek Chromite Ores and Concentrates. Murphy. March.E. John. Papp.S. JIM. Prereduction. U. August 1980. Versar. U. 350-354. Inc." Materials Transactions. August 1992. Multi-Media Assessment of the Inorganic Chemicals Industry. pp. 1985. 210. U. Industrial Environmental Research Laboratory. H. U. p. Office of Solid Waste. 1993 . Bureau of Mines. 1992. Volume 2. John. pp. "Chromium. "Pelletising-Sintering. II." From Mineral Facts and Problems.4-12. 1990.G. 1985. 139-155. Society for Mining. U. Vazarlis. Metals and Minerals 1992. No.S. and Explora tion. Papp. Personal Communication between ICF Incorporated and John Papp. and A. "Smelting Reduction Process with a Thick Layer of Slag for Producing Ferroalloys and Iron. Newly Identified Mineral Processing Waste Characterization Data Set. June 1992. R.S. M etallurgy. "Chromium.S. Lekatou. John. pp. Environme ntal Protection Age ncy. 1995. Papp. and G. 1994." From Kirk-Othmer E ncyclopedia of Ch emical Tech nology. "Ferroalloys. Environmental Protection Agency. 33.S.E. Vol VI. 4-1 . 17. Vol. pp. "Sodium Dichromate Production. "Chromium. 20." Iron and Steelmaking. 228-263. . "Developing Plasma Applications for Metal Production in the USA. 265-275. John. 325-378." Ironmaking and Steelmaking. Bureau of M ines.S. 1993.